Direct Injection Liquid Chromatography High-Resolution Mass Spectrometry for Determination of Primary and Secondary Terrestrial and Marine Biomarkers in Ice Cores

Many atmospheric organic compounds are long-lived enough to be transported from their sources to polar regions and high mountain environments where they can be trapped in ice archives. While inorganic components in ice archives have been studied extensively to identify past climate changes, organic compounds have rarely been used to assess paleo-environmental changes, mainly due to the lack of suitable analytical methods. This study presents a new method of direct injection HPLC-MS analysis, without the need of pre-concentrating the melted ice, for the determination of a series of novel biomarkers in ice-core samples indicative of primary and secondary terrestrial and marine organic aerosol sources. Eliminating a preconcentration step reduces contamination potential and decreases the required sample volume thus allowing a higher time resolution in the archives. The method is characterised by limits of detections (LODs) in the range of 0.01-15 ppb, depending on the analyte, and accuracy evaluated through an interlaboratory comparison. We find that many components in secondary organic aerosols (SOA) are clearly detectable at concentrations comparable to those previously observed in replicate preconcentrated ice samples from the Belukha glacier, Russian Altai Mountains. Some compounds with low recoveries in preconcentration steps are now detectable in samples with this new direct injection method significantly increasing the range of environmental processes and sources that become accessible for paleo-climate studies

Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH) in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent observations. This study emphasises the importance of studying the combined effects of several atmospheric parameters such as oxidants and RH to accurately describe the complex oxidation scheme of organic aerosols

Comprehensive modelling study of ozonolysis of oleic acid aerosol based on real-time, online measurements of aerosol composition

The chemical composition of organic aerosols profoundly influences their atmospheric properties, but a detailed understanding of heterogeneous and in-particle reactivity is lacking. We present here a combined experimental and modeling study of the ozonolysis of oleic acid particles. An online mass spectrometry (MS) method, Extractive Electrospray Ionization (EESI), is used to follow the composition of the aerosol at a molecular level in real time; relative changes in the concentrations of both reactants and products are determined during aerosol aging. The results show evidence for multiple non-first-order reactions involving stabilized Criegee intermediates, including the formation of secondary ozonides and other oligomers. Offline liquid chromatography MS is used to confirm the online MS assignment of the monomeric and dimeric products. We explain the observed EESI-MS chemical composition changes, and chemical and physical data from previous studies, using a process-based aerosol chemistry simulation, the Pretty Good Aerosol Model (PG-AM). In particular, we extend previous studies of reactant loss by demonstrating success in reproducing the time dependence of product formation and the evolving particle size. This advance requires a comprehensive chemical scheme coupled to the partitioning of semivolatile products; relevant reaction and evaporation parameters have been refined using our new measurements in combination with PG-AM.This work was supported by the UK Natural Environment Research Council (NERC grant NE/I528277/1) and the European Research Council (ERC starting grant 279405 and the Atmospheric Chemistry Climate Interactions (ACCI) project, grant 267760). PTG thanks NCAS Climate for support

A new electrodynamic balance design for low temperature studies

Abstract. In this paper we describe a newly designed cold electrodynamic balance (CEDB) system, which was built to study the evaporation kinetics and freezing properties of supercooled water droplets. The temperature of the CEDB chamber at the location of the levitated water droplet can be controlled in the range: −40 to +40 °C, which is achieved using a combination of liquid nitrogen cooling and heating by positive temperature coefficient heaters. The measurement of liquid droplet radius is obtained by analyzing the Mie elastic light scattering from a 532 nm laser. The Mie scattering signal was also used to characterize and distinguish droplet freezing events; liquid droplets produce a regular fringe pattern whilst the pattern from frozen particles is irregular. The evaporation rate of singly levitated water droplets was calculated from time resolved measurements of the radii of evaporating droplets and a clear trend of the evaporation rate on temperature was measured. The statistical freezing probabilities of aqueous pollen extracts (pollen washing water) are obtained in the temperature range: −4.5 to −40 °C. It was found that that pollen washing water from water birch (Betula fontinalis occidentalis) pollen can act as ice nuclei in the immersion freezing mode at temperatures as warm as −22.45 (±0.65) °C. </jats:p

Rapid interrogation of the physical and chemical characteristics of salbutamol sulphate aerosol from a pressurised metered-dose inhaler (pMDI)

Individual micron-sized solid particles from a Salamols pharmaceutical inhaler are stably captured in air using an optical trap for the first time. Raman spectroscopy of the levitated particles allows online interrogation of composition and deliquescent phase change within a high humidity environment that mimics the particle’s travel from inhaler to lun

Constructing living buildings: a review of relevant technologies for a novel application of biohybrid robotics

Biohybrid robotics takes an engineering approach to the expansion and exploitation of biological behaviours for application to automated tasks. Here, we identify the construction of living buildings and infrastructure as a high-potential application domain for biohybrid robotics, and review technological advances relevant to its future development. Construction, civil infrastructure maintenance and building occupancy in the last decades have comprised a major portion of economic production, energy consumption and carbon emissions. Integrating biological organisms into automated construction tasks and permanent building components therefore has high potential for impact. Live materials can provide several advantages over standard synthetic construction materials, including self-repair of damage, increase rather than degradation of structural performance over time, resilience to corrosive environments, support of biodiversity, and mitigation of urban heat islands. Here, we review relevant technologies, which are currently disparate. They span robotics, self-organizing systems, artificial life, construction automation, structural engineering, architecture, bioengineering, biomaterials, and molecular and cellular biology. In these disciplines, developments relevant to biohybrid construction and living buildings are in the early stages, and typically are not exchanged between disciplines. We, therefore, consider this review useful to the future development of biohybrid engineering for this highly interdisciplinary application.publishe

Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

© 2016 Author(s).Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively. We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κ$_CCN$, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH$_4$)$_2$SO$_4$, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions. In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κ$_HTDMA$, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity. Closure analysis of CCN and HTDMA data showed κ$_HTDMA$ was lower than κ$_CCN$ by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.EUROCHAMP2 European Commission 7th framework, NordForsk, VILLUM Foundatio

From the discrete to the continuous - towards a cylindrically consistent dynamics

Discrete models usually represent approximations to continuum physics. Cylindrical consistency provides a framework in which discretizations mirror exactly the continuum limit. Being a standard tool for the kinematics of loop quantum gravity we propose a coarse graining procedure that aims at constructing a cylindrically consistent dynamics in the form of transition amplitudes and Hamilton's principal functions. The coarse graining procedure, which is motivated by tensor network renormalization methods, provides a systematic approximation scheme towards this end. A crucial role in this coarse graining scheme is played by embedding maps that allow the interpretation of discrete boundary data as continuum configurations. These embedding maps should be selected according to the dynamics of the system, as a choice of embedding maps will determine a truncation of the renormalization flow.Comment: 22 page

Organic Compounds in a Sub-Antarctic Ice Core: A Potential Suite of Sea Ice Markers.

Investigation of organic compounds in ice cores can potentially unlock a wealth of new information in these climate archives. We present results from the first ever ice core drilled on sub-Antarctic island Bouvet, representing a climatologically important but understudied region. We analyze a suite of novel and more familiar organic compounds in the ice core, alongside commonly measured ions. Methanesulfonic acid shows a significant, positive correlation to winter sea ice concentration, as does a fatty acid compound, oleic acid. Both may be sourced from spring phytoplankton blooms, which are larger following greater sea ice extent in the preceding winter. Oxalate, formate, and acetate are positively correlated to sea ice concentration in summer, but sources of these require further investigation. This study demonstrates the potential application of organic compounds from the marine biosphere in generating multiproxy sea ice records, which is critical in improving our understanding of past sea ice changes

Multiphase composition changes and reactive oxygen species formation during limonene oxidation in the new Cambridge Atmospheric Simulation Chamber (CASC)

The chemical composition of organic aerosols influences their impacts on human health and the climate system. Aerosol formation from gas-to-particle conversion and in-particle reaction was studied for the oxidation of limonene in a new facility, the Cambridge Atmospheric Simulation Chamber (CASC). Health-relevant oxidising organic species produced during secondary organic aerosol (SOA) formation were quantified in real time using an Online Particle-bound Reactive Oxygen Species Instrument (OPROSI). Two categories of reactive oxygen species (ROS) were identified based on time series analysis: a short-lived component produced during precursor ozonolysis with a lifetime of the order of minutes, and a stable component that was long-lived on the experiment timescale (ĝ1/4ĝ€4ĝ€h). Individual organic species were monitored continuously over this time using Extractive Electrospray Ionisation (EESI) Mass Spectrometry (MS) for the particle phase and Proton Transfer Reaction (PTR) MS for the gas phase. Many first-generation oxidation products are unsaturated, and we observed multiphase aging via further ozonolysis reactions. Volatile products such as C9H14O (limonaketone) and C10H16O2 (limonaldehyde) were observed in the gas phase early in the experiment, before reacting again with ozone. Loss of C10H16O4 (7-hydroxy limononic acid) from the particle phase was surprisingly slow. A combination of reduced C Combining double low line C reactivity and viscous particle formation (relative to other SOA systems) may explain this, and both scenarios were tested in the Pretty Good Aerosol Model (PG-AM). A range of characterisation measurements were also carried out to benchmark the chamber against existing facilities. This work demonstrates the utility of CASC, particularly for understanding the reactivity and health-relevant properties of organic aerosols using novel, highly time-resolved techniques.This work was funded by the European Research Council (grant 279405), the UK Natural Environment Research Council (grant NE/H52449X/1), and the Velux foundation (project number 593)